JPS61276828A - Fluorine-containing ion exchange resin - Google Patents

Abstract

PURPOSE:To provide an ion exchange resin having a crosslinked structure obtained by the copolymerization of a fluorine-containing divinyl compound with a specific fluorine-containing vinyl compound, polymerizable rapidly in high polymerization yield, and having excellent heat-resistance, corrosion- resistance and dimensional stability. CONSTITUTION:The objective fluorine-containing ion exchange resin contains a crosslinked structure and obtained by the copolymerization of (A) a fluorine- containing divinyl compound and (B) a fluorine-containing vinyl compound having an ion exchange group or a functional group convertible to an ion exchange group. The component A is a perfluorodivinyl ether compound, and its amount is >=30wt% based on the whole monomer, or >=50wt% in the case of forming an ion exchange resin membrane. The component B is a fluorine- containing vinyl ether compound having an ion exchange group or a functional group convertible to an ion exchange group.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a fluorine-containing resin produced by copolymerizing a fluorine-containing divinyl compound and a fluorine-containing vinyl compound, and particularly relates to a fluorine-containing resin produced by copolymerizing a fluorine-containing divinyl compound and an ion exchange group or A membrane-like ion copolymer with a fluorine-containing vinyl monomer having a functional group that can be converted into an ion-exchange group, which has a crosslinked structure and an ion-exchange group, and which is particularly useful as a diaphragm for alkali chloride electrolysis. It provides replacement resin.

[Prior art and problems]

Japanese Patent Publication No. 41-7949 describes CF,=CF(OCF,CFY)nOCFR,C as a fluorine-containing copolymer having a functional group that can be converted into an ion exchange group by reaction.
F, 80. F (R, is fluorine or a perfluorofurkyl group having 1 to 10 carbon atoms, Y is fluorine or a trifluoromethyl group, n is an integer from 1 to 3) and tetrafluoro Copolymers such as ethylene are described. In addition, special public service 45-2630
In Publication No. 3, CF,=CFO(CF,) n-
X (in the formula, n is an integer of 2 to 12, and X is a group -CN, -COF).

-COOH, -COOR, -COOM and -〇〇NR
,R.

(R□ has 1 to 10 carbon atoms, R11 and R are one of R1, M is sodium, potassium or cesium) and an ethylene monomer, such as tetrafluoroethylene. A method for making the polymer is described.

In the copolymerization of perfluorovinyl sulfonyl fluoride or perfluorovinyl carboxylic acid ester and tetrafluoroethylene as described above, since the tetrafluoroethylene is a gaseous monomer with a boiling point of -76°C,
Polymerization is generally carried out in the presence of a radical initiator under high pressure. In addition, in such copolymerization, a stable resin with high ion exchange capacity cannot be obtained unless the molecular weight of the resulting copolymer is increased, so the concentration of the polymerization initiator must be kept low (
Further, in order to maintain the solubility of gaseous monomers such as tetrafluoroethylene, it is necessary to take measures such as stopping the polymerization rate at a stage of 20% to 30% or less. Therefore, a step of recovering and purifying the unreacted supernatant is required after polymerization. Furthermore, when producing an ion exchange membrane from a fluorine-containing monomer, the copolymer must be thoroughly washed with a solvent and then extruded into a film at a high temperature of 200°C to 250°C. As mentioned above, the production of fluorine-containing copolymers involves complicated polymerization operations, and the production of ion exchange membranes from the fluorine-containing copolymers involves two steps of polymerization and molding, which requires a large amount of equipment and operations. .

On the other hand, when a copolymer of perfluorovinyl sulfonyl fluoride or perfluorovinyl carboxylic acid ester and tetrafluoroethylene is introduced with a sulfonic acid group or a carboxylic acid group after extrusion molding, the copolymer becomes polytetrafluoroethylene. Because it is a pseudo-crosslink that utilizes the crystallinity of ethylene, it has a large ion exchange capacity (i.e., the ratio of ion exchange groups in the copolymer is large).
In some cases, it often swells significantly in pure water, alkali, aqueous salt solutions, methanol, 7-cetone, chlorine-based solvents, or fluorine-based solvents, and eventually dissolves. Therefore, for a fluorine-containing copolymer having a large ion exchange capacity and good dimensional stability, it is desired that the copolymer be crosslinked by covalent bonds rather than pseudo-crosslinking.

[Problem that the invention seeks to solve]

Regarding the production of ion exchange resins having a crosslinked structure, for example, Japanese Patent Publication No. 57-53371゜57-53372 describes the general formula CF of perfluorocarbon vinyl ether.
, = CF"-0-(CF,)n-X (wherein, n is an integer of 2 to 12, X is -CN, -COF, -COOH,
-COOR, -COOM or 100NR, R8, where R is an alkyl group.

(respectively R2, R, is hydrogen or R, M is sodium, potassium or cesium) or the general formula CF,=CFC
OZ (in the formula, 2 is fluorine, flukoxy group, 7j) group,
hydroxy group) and, together with tetrafluoroethylene, the general formula CF, =
CF-〇-c-CF, CF, -0) tCF=
Although it has been suggested to use a diolefin such as CF, (in the formula, t is an integer of 2 to 20), there are no specific disclosures such as examples. However, when producing a fluorine-containing copolymer containing tetrafluoroethylene as the main copolymerization monomer component, it is difficult to produce a fluorine-containing vinyl compound having such an ion-exchange group or a functional group that can be converted into an ion-exchange group. As mentioned above, the tetrafluoroethylene is a gaseous monomer with a boiling point of -76°C, and it is extremely easy to polymerize, the polymerization rate is high, and the heat of polymerization is quite large, so the polymerization operation is complicated, and the fluorine-containing There is also the problem that a large amount of equipment and operations are required when obtaining a membrane-like ion exchange resin from a copolymer.

[Means to solve the problem]

In view of the above, the present inventors have conducted intensive research on the production of ion exchange resins having a crosslinked structure. As a result of copolymerizing the compound with the compound as the main copolymerization monomer component, it was unexpectedly found that polymerization was quickly achieved at a high polymerization rate, and a desired fluorine-containing ion exchange resin having a crosslinked structure was obtained, and the present invention was realized. This is what we have come to offer. That is, the present invention is a fluorine-containing ion exchange resin having a crosslinked structure, which is obtained by copolymerizing a fluorine-containing divinyl compound and a fluorine-containing vinyl compound having an ion exchange group or a functional group convertible to an ion exchange group.

In the present invention, as a fluorine-containing vinyl compound having a functional group that can be converted into an ion exchange group,
CF3 I CF = CFOCF CFOCF, CF, 80. F
g and CF, =CFO(CF, ), C00CH
, respectively, the infrared absorption spectra (
IR) are shown in Figure 1 and Figure tJ2, respectively. The IR of the ion exchange resin obtained by copolymerizing mainly with tetrafluoroethylene instead of perfluorodivinyl ether is 638-1 and 625-1, 10F,
Although there is a large characteristic absorption due to CF,-,
In Figures 1 and 2, no such absorption is observed, and 1
The absorption pattern between 300 and 700 cm is also completely different.
Indicates that it is a different type of structure.

The structure of the ion-exchange resin in the present invention is a three-dimensionally crosslinked resin, so it has a complex network structure of seven mer units, so the resin structure cannot be easily expressed, but it can be expressed by the following formula. It has a structure in which constituent units are randomly intertwined through radical polymerization.

(In the formula, R, , R; are fluorine-containing alkylene, and 2 is an ion exchange group) In the present invention, the fluorine-containing divinyl compound is CF, =CF, OCF, CF20CF=CF.

As a result of confirming the structure of the ion-exchange resin obtained using C.C. using a molecular model, the following cyclic structure can be formed, although the degree of cyclization is unknown. Presumed.

Hereinafter, the present invention will be explained in detail including the manufacturing method.

Examples of the hepta-hair-containing divinyl compound constituting the fluorine-containing polymer having a crosslinked structure of the present invention include CF8 CF and -CF (CF2). ~1o (OCFCF2). ~
,0CF-CF',.

At least 11 compounds represented by CF, -CF(CF2), 1oCF-CF8, etc.

Examples of the fluorine-containing vinyl monomer having an ion exchange group or a functional group convertible to an ion exchange group include CF8 CF2-CFO (CF, CFO). ~8(CF2)2~
BSOgX (X is Cz, F, OH, 0CH8, OC,
I'l,,ONa.

OK, NH,, -NHCH, CH, NH2, -NHCH
, CM.

N+CCH3)8C1-).

C.F.

0F, -CFO(CF,CFO), ~5(CFl)1~
．． Y.

CF, -CFO (CF, CFO). ~8 (CF2 >
2~,0CFY.

CF8 CF, -CFO (CF, CFO). ~, (C
F, CF, 0) 1-8CF, Y (Y is -CN,
-COF, -COOH, -COOR,.

-COOM, -CONR,R,, -CONHCH,CH
,NH.

and -CONHCH,CH,N+(CH,') 8CL
-, where 80 is a furkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, each of R8 and R8 is hydrogen or one of Ro, and M is sodium,
potassium or cesium).

CF, -CFCOOCH8, CF, -CFCOF, CF
,-〇FSO,F.

CF, -CFO(CF,), ~, P(OCH8),
.

CF = CFOCF, (CF, CF,), ~, H.

It is at least one kind of compound represented by CF -CFO (CF, CF, ), ~, ■.

In the present invention, in order to obtain a desired ion exchange resin having a crosslinked structure, the type of fluorine-containing divinyl compound and the fluorine-containing vinyl compound having an ion exchange group or an egg group convertible to an ion exchange group are used. Although different, it is extremely important to maintain the fluorodivinyl compound generally at a proportion of 30% or more by weight based on the total monomers. That is, in a monomer mixture of a fluorine-containing compound having an ion exchange group or a functional group convertible to an ion exchange group and a fluorine-containing divinyl compound, the charging ratio of the fluorine-containing divinyl compound is increased to 30% by weight or more. 1 The polymerization rate can be increased, and a polymer with a three-dimensional crosslinked structure can be obtained at a high polymerization rate. On the other hand, if the proportion of the fluorine-containing divinyl compound charged is less than 30% by weight, the polymerization rate will be low and an ion exchange resin having the desired crosslinked structure cannot be obtained. In addition, as the charging ratio of the fluorine-containing divinyl compound is increased to 30 mol% or more, the exchange capacity of the obtained ion exchange resin decreases, so it is generally preferable to keep it at 90 mol% or less in consideration of the exchange capacity. .

Furthermore, since ion exchange membranes for salt electrolysis are generally used under harsh conditions in high-temperature, high-concentration alkali and salt aqueous solutions, it is essential that the membrane has a dense structure. Therefore, in the fluorine-containing membrane ion exchange resin of the present invention, it is preferable that the proportion of the fluorine-containing divinyl compound added to the total monomers is 50% by weight or more. That is, in the case of a fluorine-containing ion exchange membrane in which the ratio of the fluorine-containing divinylated metal to the total monomers is less than 50% by weight, the desired current efficiency cannot be obtained. on the other hand,
As the content of the fluorine-containing divinyl compound in the total monomer increases, the ion exchange capacity of the fluorine-containing ion exchange membrane decreases and the membrane resistance increases, so the charging ratio is 90%.
It is preferable that it is below.

According to the present invention, the charging ratio of the fluorine-containing vinyl compound having an ion-exchange group or a functional group convertible to an ion-exchange group and the fluorine-containing divinylated metal material can be varied over a wide range. 0 per resin I
．． There is an advantage that an ion exchange resin having a high exchange capacity can be easily produced from a low exchange capacity of 0.01 to 4 meq (hereinafter also referred to as Kmeq/i).

Furthermore, in addition to the above-mentioned fluorine-containing vinyl compound, CF may be added if necessary.

CF,=CFO(CF,CF). ~80R, (R is a perfluorofurkyl group having 1 to 10 carbon atoms).

CF, ICF, , C-〒CFCt, CF8CF=CF,
.

Fine powder of fluorine-containing monomers such as CF = CFH, CF, =CH, polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and flukyl vinyl ether, etc.

Oligomer or perfluorohexane.

It is also possible to polymerize by adding a solvent such as barfluoropobutane, polyfluoroether, trichlorotrifluoroethane, and barfluoropolyether.

In the present invention, as an initiator for copolymerizing a fluorine-containing divinyl compound and a fluorine-containing vinyl compound having an ion exchange group or a functional group convertible to an ion exchange group, benzoyl peroxide, lauroyl peroxide, imbutyryl peroxide, etc. diacyl peroxide,
Cumene hydroperoxide.

Hydroperoxide such as t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, difurkyl peroxide such as trichlor 7-cetyl peroxide, t-butyl peroxyneodecanoate, t-butyl peroxide, etc. Flukyl peresters such as luperoxybiplate, bis(4-t-butylcyclohexyl)peroxydicarbonate, bar carbonates such as diisopropylperoxydicarbonate, azobiswingtyronitrile, 7zobiscyclohexanecarbonitrile, etc. 7zo-based initiator, succinic acid peroxide, general formula B(CF,)mCOOC(CF,)r
nB.

Ct(CF, CFCt)nCF, C00CCF, (C
FCtCF, ) nC1 (where B is hydrogen or fluorine atom; 9m is 1-24; h is 1-1G). Dipentafluoropropionyl peroxide.

ditetrafluoroppionyl peroxide, dihebutafluoroptyryl peroxide, di(trichlorooctafluorohexamyl)peroxide, di(tetrafluorodecafluorooctanoyl)peroxide, ciba-fluoro-2-n-pionyl peroxide Fluorine-containing diacyl peroxides such as p-booxypropionyl peroxide, diperfluoro a-2-inpropoxypropionyl peroxide, NF, NF, N, F, etc.

B　　　　　z　4 CF2O(NF,)=C(NF,)CF8.

It is possible to use a fluorine-containing nitrogen compound such as CF30F(NF2)C(NF)CF8, an initiator such as potassium persulfate or ammonium persulfate, or ultraviolet rays or ionizing radiation. Among these polymerization initiators, those that are soluble in the monomer mixture solution, whose half-life temperature is below the boiling point of the used nanatsumer under normal pressure, and which can form a crosslinked resin with a high polymerization rate. An initiator is required. Initiators that meet these conditions include fluorine-containing diacyl peroxide and peroxydicarbonate.

CF2O(NF,)=C(NF,)CF8.

It is preferable to use one or more polymerization initiators such as CF CF (NF ) C (NF) CF8. The amount of these initiators added is 0.1 to 10% by polymerization based on seven polymers,
Preferably it is 0.5 to 5% polymerization. Note that it is also possible to use these initiators after diluting them with an organic solvent.

The polymerization temperature is -80°C to 400°C, preferably -10°C to
The temperature is 150° C., and the polymerization temperature may be raised stepwise to complete the polymerization. In addition, polymerization is carried out in the presence of an inert gas such as nitrogen at a temperature of -70waaHli to 20
Preferably, it is carried out under a pressure of KP/cit. The form of polymerization may be any method such as bulk polymerization, solution polymerization, suspension polymerization, etc. Bulk polymerization, which reaches high polymerization rates, is preferably recommended for the polymerization of ion exchange membranes.

During the above bulk polymerization, polytetrafluoroethylene, a copolymer of ethylene and tetrafluoroethylene, and a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether are used.

Fluorination of copolymers of tetrafluoroethylene and perfluorovinylsulfonyl fluoride, copolymers of tetrafluoroethylene and perfluorovinylcarboxylic acid esters, Guifoil (manufactured by Daikin Industries), Fontprin oil (manufactured by Monte Edison), etc. By adding a fine powder or a low molecular weight polymer made of oil, polyvinylidene fluoride, etc., the viscosity of the polymerization solution and the flexibility of the resulting film can be adjusted.

Also, during bulk polymerization, polytetrafluoroethylene, a copolymer of ethylene and tetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, a copolymer of tetrafluoroethylene and perfluorovinyl sulfonyl fluoride.

Fabrics, nets, and other woven fabrics and nonwoven fabrics made of copolymers of tetrafluoroethylene and perfluorovinylcarboxylic acid esters, polyvinylidene fluoride, polyvinyl chloride, polypropylene, etc.

Nets, films, porous films, tubes, etc. can be used as reinforcing materials or supports during polymerization.

In addition, the above tetrafluoroethylene)
or fibers made of tetrafluoroethylene treated with metallic sodium, or fibers made of tetrafluoroethylene with tetrafluoroethylene and perfluoroalkyl vinyl ether, tetrafluoroethylene and perfluorovinyl sulfonyl fluoride, tetrafluoroethylene and perfluorovinyl carbon ester, etc. It is also possible to use a fabric obtained by impregnation polymerization or graft polymerization of one kind in the presence of a radical polymerization initiator or radiation.

Or stainless steel, titanium, or nickel.

A metal such as a wire mesh made of platinum, punched metal, or a sintered plate can be used as the reinforcing material.

In order to obtain particulate resin from the resin produced in this manner, the bulk polymer can be processed into particulate form by cutting or crushing. Further, by copolymerizing a fluorine-containing divinyl compound and a fluorine-containing vinyl compound having an ion exchange group or a functional group convertible to an ion exchange group in a fluorine-containing solvent while stirring in the presence of a polymerization initiator, particulate Ion exchange 11 fat or its precursor can be obtained.

Furthermore, in the present invention, in order to obtain a membrane-like ion exchange resin, (1) a block polymer polymerized into a cylindrical shape is cut;

(2) Casting the mixture of seven snails onto a flat plate and polymerizing it.

(3) Pour the mixture of nanatsumer into the space between the slits and polymerize.

(4) A viscous 7-mer mixture obtained by polymerizing the monomer mixture to some extent is applied to a reinforcing material made of polytetrafluoroethylene, and both sides are sandwiched between films of tetrafluoroethylene, stainless steel, polyester, polyvinyl alcohol, polyethylene, etc. Polymerize. Furthermore, the surface of the polymerized film is roughened by polymerizing using a release film roughened by subjecting such a release film to a blast treatment or a grinding treatment.

(5) A low polymer obtained by polymerizing the seven-mer mixture to some extent is coated on a reinforcing material made of tetrafluoroethylene using a doctor knife or the like, and then sandwiched between release films and polymerized.

(6) A drum in which a reinforcing material made of tetrafluoroethylene and a release film are concentrically wound is placed in an autoclave, and after evacuating the drum, the degassed monomer mixture is injected into the autoclave and polymerized.

(7) Presence of a monomer mixture of the same type or a different type, or a monomer mixture obtained by partially polymerizing them, on a film-like material obtained by polymerizing a monomer mixture, or a mixture of these monomers. A film-like material having a multilayer structure is obtained by superimposing films impregnated with and then polymerizing them.

(8) A fluorine-containing ion exchange membrane or a fluorine-containing base ion exchange membrane is immersed in a 7-mer mixture, and then sandwiched between films such as polytetrafluoroethylene for impregnation polymerization.

In addition, the monomer mixture is a fluorine-containing dibitual compound,
It is a solution containing a polymerization initiator and a fluorine-containing vinyl compound having a functional group that can be converted into an ion, a substituent, or an ion exchange group.

In order to introduce ion exchange groups into the copolymer obtained in this way, K is hydrolyzed using an alkaline solution of KOH or NaOH to obtain a cation exchange resin or a cation exchange resin membrane. It will be done. Or again,
It is also possible to convert the sulfonyl halide group or carbonyl I-ride group into an anion exchange group by treating it with a polyamine such as ethylenediamine to form an anion exchange resin, a strong ion exchange resin membrane, or a bipolar membrane. Furthermore, some or all of the resin can be converted into carboxylic acid groups by acting on the copolymer having sulfonyl chloride groups with an oxidizing agent or reducing agent, or by irradiating the sulfonic acid groups with ultraviolet rays in the presence of NO3 and NO gas. Can be converted.

The ion exchange membrane obtained by the method described above can be ground and solidified on the surface of the membrane. Also T i
O2Z r OB - Rub, a thin film made of polytetrafluoroethylene or the like.

-In, 06-polytetrafluoroethylene.

A thin film made of N1-polytetrafluoroethylene, pt-polytetrafluoroethylene, etc.

A vapor-deposited metal film or the like can be bonded to one or both sides of the film.

The ion exchange resin having a crosslinked structure of the present invention has excellent properties such as heat resistance, corrosion resistance, and one-dimensional stability, so it can be applied to various fields. For example, gaskets, spacers, coating materials, ion exchange resins, adsorbents.

As a catalyst for hydrolysis of esters, dehydration of alcohols, hydration of olefins, synthesis of peracids, etc., and as a carrier for chemically modified electrons, conductive metal compounds, etc.

Electrolysis, fuel cells, bar evaporation, gas separation, reverse osmosis, diffusion dialysis, electrodialysis.

It can be used as a diaphragm for ultrafiltration, etc., and further as an electrolytic diaphragm for alkali chloride.

〔effect〕

The ion exchange resin having a crosslinked structure of the present invention is an ion exchange resin that is copolymerized with conventional tetrafluoroethylene as a main component to a fluorine-containing vinyl compound having an ion exchange group or a functional group that can be converted into an ion exchange group. It is possible to obtain higher exchange capacities than resins and also NaOH
Dimensional changes are small in aqueous solutions, KOH aqueous solutions, alcohol, water, and fluorinated solvents. Therefore, the membrane-formed ion exchange resin of the present invention has the characteristics of high ion conductivity, selective permeability, and mechanical strength, and is therefore extremely useful as a diaphragm for electrolysis of aqueous alkaline salt solutions.

〔Example〕

Examples of the present invention will be described in more detail below, but it goes without saying that the present invention is not limited to such explanations.

Example 1 CF, -〇F, OCF, CF, 0 in a glass ampoule
CF=CF, (purity 98%) and CF8 CF2=CFOCF, CFOCF, CF, So, F (
The monomers (purity 99%) shown in Table 1 were added in their entirety as shown in Table 1, and as a gluten opener (CF, CF).

After charging CF, IC00)2 to 3% by weight of the total monomers, nitrogen substitution was repeated under reduced pressure under dry ice and methanol, and a glass ampoule was melt-sealed.
After polymerizing for 3 days at
The polymerization rate of the polymer was determined by immersing it in J-trifluorop-equun, filtering it using a glass filter, and drying it under reduced pressure while heating. The results are shown in Table 1.

When a part of this polymer was cut into a thin film and its IR spectrum was measured, there was no absorption due to perfluorovinyl ether groups, but absorption due to perfluorosulfonyl fluoride groups was observed at 1475 cm 2 .

Also, since the polymerization rate is high, barfluorodivinyl ether is CF.

It is clear that cross-linking polymerization occurs with CF, -CFOCF, CFOCF, CF, So, and F at a high polymerization rate.

Furthermore, 15 parts by weight of NaOH was added to this overlay.

A cation exchange resin of sodium sulfonate was obtained by treatment with a hydrolysis solution consisting of 30 parts by weight of dimethyl sulfoxide and 55 parts by weight of water at 90°C for 6 hours. The exchange capacity in the resin was determined by elemental analysis of sulfur in this cation exchange resin. The results are also shown in Table 1.

Comparative example 1 As in Example 1, CF, =CFOCF, CF.

When polymerization was carried out by reducing the proportion of 0CF=CF in the total monomers, a viscous polymer could be obtained, but a good three-dimensionally crosslinked polymer could not be obtained. The results are also shown in Table 1.

Example 2 As in Example 1, CF,=CF,0(CF,).

0CF=CF, (95% purity) and CFB=CFOCF
.

Predetermined amounts of each of the seven compounds shown in Table 2, consisting of CF, CFOCF, CF, So, and F (purity 99%), were added as an initiator (CF, CF, CF, Coo) to 2λ of the edible compound. % by weight, polymerization was carried out at 20° C. for 2 days, and the polymerization rate was determined. Furthermore, the ion exchange capacity in the resin was determined by elemental analysis of the hydrolyzed sulfur of this polymer. The results are also shown in Table 2.

ratio)! 2 Example 2 ゛Example 91J Same as 2, CF,=CFO(CF2),
When polymerization was carried out using a small proportion of 0CF=CF in the total monomers, a three-dimensionally crosslinked polymer with a high polymerization rate was not obtained. This result is also shown in Table 2.

Examples 3 to 17 Constant polymerization of various perfluorodivinyl compounds as shown in Table 3 and various perfluorovinyl ethers having a functional group that can be converted into an ion exchange group using the initiators also shown in Table 3. Polymerization was carried out under the following conditions, and the polymerization rate and exchange capacity were determined in the same manner as in Example 1. When the cation exchange group was of the carvone WI type, the copolymer obtained by polymerization was subjected to elemental analysis, and the exchange capacity was calculated from the composition ratio. It was clear that the obtained copolymer had a crosslinked structure based on barfluorovinyl ether groups (there was no absorption of 1840cIR). Tomo purity 95~l
OO% was used.

Example 18 CF8 ■ CF, = CFOCF, CFOCF, CF, SO□F (purity 991yo), CF = CFOCFsCF 5Oc
F=cF s (purity 98%'), (CF80F, C
F, C00), respectively, were placed in a stainless steel autoclave in the prescribed amounts shown in Table 4, and placed in dry ice/meta/
After purging with nitrogen under reduced pressure under a vacuum chamber, the polytetrafluoroethylene ring was applied to a cloth with a thickness of 0.10 mm, and both sides of the cloth were sandwiched between polytetrafluoroethylene ring films.
Polymerization was carried out for 1 day at 20"C under nitrogen pressure of y/cr&. After polymerization, the parent ion exchange membrane was taken out from the release film and hydrolyzed by the method of Example 1 to obtain a cation exchange membrane with sulfonic acid groups. Using this cation exchange membrane,
Two-room electrolytic cypress (effective area: 50 d, anode ruthenium dioxide coated titanium electrode.

Cathode: Iron 1 Distance between membrane and cathode: 4im, membrane and anode in close contact,
Solve '1 Temperature: 90℃, current density = 30A/dyl
) was used to supply a 5N NaCl aqueous solution to the anode chamber and water to the cathode chamber to produce a 30% aqueous sodium hydroxide solution. The results are shown in Table 4. Comparative Example 3 Regarding the electrolytic results of a cation exchange membrane synthesized in the same manner as in Example 18 by reducing the content of CF,=CFOCF2CF,0CF=CF, in the total monomers. Also shown in Table 4. CF2=cF.

It is clear that when the content of CF2CF, 0CF=CF2 in the total monomers decreases, it no longer functions as a diaphragm for dissolving alkali +, +.

Example 19 CF = CFOCF OF C00CH, (purity 97B
! 12%) 3.5 parts by weight, CF2=CFOCF2CF, 0C
F=CF.

(Purity 97%) 6.5 parts by weight, (CF, CF, CF.

Coo), 0.4 parts by weight of the monomer mixture was purged with nitrogen at low temperature and reduced pressure, and then impregnated into a porous film made of polytetrafluoroethylene with a thickness of Q, l II+ (manufactured by Sumitomo Electric Industries = Fluorobor). Then, polymerization was carried out at 20° C. for 1 day in a nitrogen atmosphere using a 100 μm stainless steel thin film whose surface was roughened by the Sandgelast method as a release material. After polymerization, the base ion exchange membrane was taken out and hydrolyzed by the method of Example 1 to synthesize a carboxylic acid type cation exchange membrane. The exchange capacity of this membrane was measured by neutralization titration method.
When the weight of the fluorobore was subtracted from the weight of the membrane, it was found to be 1.3 meq/! It was i'. When the surface of this film was observed using a scanning electron microscope, fine irregularities were found. When this film was electrolyzed in the same manner as in Example 18, the sliding voltage was 3.32V.

The current efficiency was 93%.

Example 20 CF = CFO (CF, ), C00CH, (purity 97%
)3 parts by weight, CF,=CFOCF,CF,0CF=C
F.

(Purity 98%) 7 parts by weight, (CF80F, CF.

A 7-mer mixture consisting of 20.2 parts by weight of Coo) was purged with nitrogen at low temperature and reduced pressure, and then impregnated into a 0.1 inch thick porous film made of polytetrafluoroethylene (Fluop Pore, manufactured by Sumitomo Electric Industries). The membrane was sandwiched between tetrafluoroethylene films on both sides, and polymerized at 20° C. for 1 day in a nitrogen atmosphere to synthesize the first layer of the base cation exchange membrane.

Furthermore, a monomer mixture consisting of CF = CFO (CF, ), C00CR84 overlapping part, CF = CFOCF, CF, 0CF = CF, 6 overlapping part, (CF80F, CF, C00), 0.2 parts by weight, The above porous film and the first
The parent cation exchange membranes of each layer were stacked and immersed at 0°C for 2 hours, then sandwiched between polytetrafluoroethylene films on both sides and polymerized at 20°C for 2 days in a nitrogen atmosphere. After polymerization, the base ion exchange membrane consisting of two layers is taken out,
Hydrolysis was carried out by the method of Example 1 to synthesize a carboxylic acid wet cation exchange membrane.

When this film was subjected to electrolysis using the method of Example 18 with the first No.
%Met.

Example 21 CF8 ■ CF = CFOCF CFOCF, CF, So, F (
Purity S 99%) 4, CF, = CF'OCF, CF.

CF　CF=CF, (purity 98%) 6 parts by weight.

(CF, CF, Coo), a monomer mixed solution consisting of 0.3 parts by weight was replaced with nitrogen under reduced pressure at a low temperature, and then a porous film made of polytetrafluoroethylene with a thickness of 0.1 mm (manufactured by Sumitomo Electric Industries, Ltd.: Fluopo After impregnating the bore) and winding it up on a stainless steel drum using polytetrafluoroethylene film as a release material, 6 to 9/cr/i
f) Polymerization under nitrogen pressure at 20"C for 1 day, then at 200"C.
The temperature was raised to ℃ over 18 hours to synthesize a base ion exchange membrane serving as the first eyelet. Furthermore, CF = CFOCF, CF
, C00Cf (83i parts.

CF, =CF, OCF, CF, 0CF=CF, 7 parts by weight.

(OF8CFICoo), a monomer mixture consisting of 0.3 parts by weight is further stretched to form a film with a thickness of 0.04 ml and a first layer of the base ion exchange membrane. After being immersed at ℃ for 2 hours, the above base ion exchange membrane and fluoropore impregnated with the 7-mer 1 mixture were wound up on a stainless steel drum using a polytetrafluoroethylene film as a release material. Polymerization was carried out at 20° C. for 1 day under an N voltage of d, and then the temperature was raised to 150° C. over 16 hours to complete the polymerization. After polymerization, the base ion exchange membrane having a two-layer structure was taken out and hydrolyzed using the method of Example 10.

The laminate part did not peel off.

When both surfaces of the membrane are observed by IR, one surface has l 67
There is a cationic cross-linking group consisting only of perfluorocarboxylic acid potassium groups derived from 73, and the other surface has a perfluorosulfone modified sodium group derived from 1060α-1 as its main component, with some perfluorocarboxylic acid groups. It turned out that it was a cation exchange membrane that existed. When this film was electrolyzed using the method of Example 18 with the surface consisting only of sodium carboxylate groups facing the cathode side, the sliding voltage was 3.
24V.

Current efficiency was 97%.

Example 22 C.F.

CF, = CFOCF, CFOCF, CF, So, F (pure & 99% > 4xiks, cp, = cpoc
p, cp.

0CF=CF', (99% purity) 5 parts by weight.

A mixed solution consisting of 80.2 parts by weight of (CF8CF, 000) was placed in a stainless steel-lined autoclave, and the mixture was replaced with chlorine under reduced pressure under dry ice and methanol, and then tetrafluoroethylene was introduced under reduced pressure and the temperature was adjusted to 1 at 0°C. ? /crIt. On the other hand, the tetrafluoroethylene cloth and polytetrafluoroethylene film wound together on a stainless steel drum were placed in a stainless steel autoclave, the autoclave was evacuated using a vacuum pump, and the above seven-mer mixture was poured into a stainless steel autoclave. was introduced into an autoclave under reduced pressure, and the monomer was held on a cloth made of tetrafluoroethylene. After that, the polymerization was completed by polymerizing at 0°C for 3 days, and the parent ion exchange membrane was taken out.
Hydrolysis was carried out by the method of Example 1. The effective resistance of this film is 0
．． 9Ωd, ion exchange capacity is 0.81 meq
/ It was 11.

[Brief explanation of drawings]

Figure 1 is CF. CF, = CFOCF, CFOCF, CF, So, Infrared absorption spectrum of an ion exchange resin obtained from a copolymer of F and perfluorodivinyl ether, Figure 2 shows CF, =
CFO (CF,), C00CH. The figure shows an infrared absorption spectrum of an ion exchange resin obtained from a copolymer of perfluorodivinyl ether and perfluorodivinyl ether.

Claims (5)

[Claims] (1) Fluorine-containing ion exchange resin having a crosslinked structure obtained by copolymerizing a fluorine-containing divinyl compound and a fluorine-containing vinyl compound having an ion exchange group or a functional group that can be converted into an ion exchange group (2) The fluorine-containing divinyl compound is 3% of the total monomers.
The fluorine-containing ion exchange resin according to claim 1, which has a content of 0% by weight or more. (3) The amount of fluorine-containing divinyl compound is 5 based on the total monomers.
The fluorine-containing ion exchange resin according to claim 1, wherein the content is 0% by weight or more and the fluorine-containing ion exchange resin is in the form of a film. (4) The fluorine-containing ion exchange resin according to claim 1, wherein the fluorine-containing divinyl compound is a perfluorodivinyl ether compound. (5) Claim 1, wherein the fluorine-containing vinyl compound having an ion exchange group or a functional group convertible to an ion exchange group is a fluorine-containing vinyl ether compound having an ion exchange group or a functional group convertible to an ion exchange group. Fluorine-containing ion exchange resin described in section